CN116742278B - Separator, preparation method thereof, electrochemical cell using separator and electricity utilization device - Google Patents
Separator, preparation method thereof, electrochemical cell using separator and electricity utilization device Download PDFInfo
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- CN116742278B CN116742278B CN202311020011.1A CN202311020011A CN116742278B CN 116742278 B CN116742278 B CN 116742278B CN 202311020011 A CN202311020011 A CN 202311020011A CN 116742278 B CN116742278 B CN 116742278B
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- gel polymer
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- copolymerization product
- separator
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
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- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application provides a separation membrane, a preparation method thereof, an electrochemical cell using the separation membrane and an electric device. The barrier film includes: a base film; and a coating body distributed on at least one side of the base film; wherein, the coating body comprises fluid and a solidifying layer coated on the periphery of the fluid; the fluid comprises gel polymer electrolyte, the gel polymer electrolyte comprises a copolymerization product of siloxane monomers and acrylic ester monomers and electrolyte adsorbed to the copolymerization product, and the copolymerization product has a hyperbranched structure; the cured layer is formed by curing the gel polymer electrolyte. The isolating film can release gel polymer electrolyte fluid in the coating body through a normal temperature lamination process so as to be bonded with the electrode pole piece, thereby avoiding the problem of isolating film wrinkling or bubbling caused by a hot-pressing compounding process. In addition, the gel polymer electrolyte fluid not only has good mechanical properties, but also can replace organic electrolyte, thereby improving the mechanical properties of the separator and the safety performance of the battery.
Description
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a separation membrane, a preparation method thereof, an electrochemical battery using the separation membrane and an electric device.
Background
In recent years, electric devices powered by secondary batteries have been widely used and popularized in industries such as various electronic products and new energy automobiles. Whereby higher demands are made on the performance of the battery.
The separator is one of the key inner layer components of the secondary battery. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film. In the process of battery preparation, it is generally necessary to thermally press the separator and the electrode tab at a relatively high temperature to bond the separator and the electrode tab. However, if the heat resistance and the adhesive property of the separator are not good, wrinkles or blisters are easily formed on the surface of the electrode sheet after hot pressing, thereby deteriorating the safety performance of the battery. Thus, the existing barrier films remain to be improved.
Disclosure of Invention
The first aspect of the present application provides a separator film comprising a base film; and a coating body distributed on at least one side of the base film. Wherein, the coating body comprises fluid and a solidifying layer coated on the periphery of the fluid; the fluid comprises gel polymer electrolyte, the gel polymer electrolyte comprises a copolymerization product of siloxane monomers and acrylic ester monomers and electrolyte adsorbed to the copolymerization product, and the copolymerization product has a hyperbranched structure; the cured layer is formed by curing the gel polymer electrolyte.
Without intending to be limited by any theory or explanation, the separator of the present application includes a base film and a coating body, can achieve normal temperature adhesion of the separator and an electrode sheet, and allows the separator to have good mechanical properties.
Specifically, the coating body comprises a fluid and a curing layer, wherein the curing layer is formed by curing the gel polymer electrolyte, and the curing layer can be broken to release the gel polymer electrolyte fluid in the normal-temperature lamination process of the isolating film and the electrode pole piece. The gel polymer electrolyte fluid can play a role of a binder, so that the isolating membrane and the electrode pole piece are firmly bonded together, and the normal-temperature bonding of the isolating membrane and the electrode pole piece is realized. In addition, the gel polymer electrolyte comprises a copolymerization product of a siloxane monomer and an acrylic monomer, wherein the copolymerization product is obtained by copolymerizing the siloxane monomer and an acrylic monomer and forming a hyperbranched structure. The molecular chain of the copolymerization product with the hyperbranched structure has a three-dimensional network structure, the molecular chain is not easy to be entangled, the viscosity is not obviously improved along with the increase of the molecular weight, and therefore, the mechanical property of the copolymerization product can be obviously improved, and the mechanical property of the isolation film is improved; and the copolymerization product can keep a viscous state at normal temperature, thereby being beneficial to the normal temperature adhesion of the isolating film and the electrode pole piece.
Moreover, the gel polymer electrolyte can replace liquid organic electrolyte, so that the isolating film is applied to a secondary battery, and the safety risk of the battery can be further reduced.
In any embodiment of the first aspect of the present application, the separator meets preset conditions, the preset conditions including: applying positive pressure to the barrier film through the test plate at 25 ℃; when the positive pressure born by the isolating film is 0.5-2MPa, the solidified layer breaks.
In any embodiment of the first aspect of the application, the siloxane monomer comprises a combination of a C10-C20 alkyl trimethoxysilane and a gamma-methacryloxypropyl trimethoxysilane.
In any embodiment of the first aspect of the application, the acrylic monomer comprises an alkyl methacrylate.
In any embodiment of the first aspect of the present application, the acrylic monomer includes at least one of methyl methacrylate, butyl methacrylate.
In any embodiment of the first aspect of the application, the electrolyte comprises an electrolyte lithium salt and an organic solvent.
In any embodiment of the first aspect of the application, the cured layer is formed from a gel polymer electrolyte that is uv cured.
In any embodiment of the first aspect of the application, the gel polymer electrolyte further comprises a photoinitiator.
In any embodiment of the first aspect of the application, the copolymerization product has a glass transition temperature Tg of 20 ℃.
In any embodiment of the first aspect of the application, the glass transition temperature Tg of the copolymerization product is less than or equal to 0 ℃.
A second aspect of the present application provides a method for producing the release film of the first aspect, comprising:
providing a gel polymer electrolyte, wherein the gel polymer electrolyte comprises a copolymerization product of a siloxane monomer and an acrylic ester monomer and an electrolyte adsorbed to the copolymerization product, and the copolymerization product has a hyperbranched structure;
a coating step including coating a gel polymer electrolyte on a surface of a base film to form a plurality of coated bodies on the surface of the base film;
and a curing step, comprising curing the gel polymer electrolyte on the surface of the coating body to obtain the isolating film.
In any embodiment of the second aspect of the present application, there is provided a gel polymer electrolyte comprising:
providing a copolymerization product;
and uniformly mixing the copolymerization product and the photoinitiator, and then soaking the mixture into the electrolyte so that the electrolyte is adsorbed on the copolymerization product to obtain the gel polymer electrolyte.
In any embodiment of the second aspect of the application, the mass ratio of copolymerization product to photoinitiator is (100:1) - (100:8).
In any embodiment of the second aspect of the application, there is provided a copolymerization product comprising:
the preparation of the linear copolymer comprises the steps of polymerizing acrylate monomers and gamma-methacryloxypropyl trimethoxy silane in the presence of an initiator to obtain the linear copolymer;
the preparation of the hyperbranched copolymer comprises the steps of subjecting a linear copolymer, C10-C20 alkyl trimethoxysilane and gamma-methacryloxypropyl trimethoxysilane to hydrolytic condensation reaction in the presence of an organic acid to obtain the hyperbranched copolymer;
and the end capping step comprises the step of mixing the hyperbranched copolymer with an end capping agent so as to enable the end capping agent to react with hydroxyl groups of the hyperbranched copolymer to obtain a copolymerization product.
In any embodiment of the second aspect of the application, the step of preparing the linear copolymer comprises:
100 parts by mass of acrylic monomer and 8-25 parts by mass of gamma-methacryloxypropyl trimethoxy silane are polymerized in the presence of 7-18 parts by mass of initiator to obtain linear copolymer.
In any embodiment of the second aspect of the application, the step of preparing the hyperbranched copolymer comprises:
subjecting 100 parts by mass of a linear copolymer and 2-25 parts by mass of C10-C20 alkyl trimethoxysilane to hydrolytic condensation reaction in the presence of an organic acid to obtain a mixed solution containing an intermediate product;
and adding 20-30 parts by mass of gamma-methacryloxypropyl trimethoxy silane into the mixed solution to enable the intermediate product and the gamma-methacryloxypropyl trimethoxy silane to undergo hydrolytic condensation reaction to obtain the hyperbranched copolymer.
In any embodiment of the second aspect of the present application, the capping step comprises:
100 parts by mass of the hyperbranched copolymer and 30-40 parts by mass of the end-capping agent are mixed so as to enable the end-capping agent to react with the hydroxyl groups of the hyperbranched copolymer, and a copolymerization product is obtained.
In any embodiment of the second aspect of the present application, the curing step comprises:
exposing the coated body to a temperature of from 1 to 10mW/cm at a temperature of from 20 to 30 DEG C 2 And (3) under ultraviolet light for 1-3min to solidify the gel polymer electrolyte on the surface of the coating body to obtain the isolating film.
A third aspect of the application provides an electrochemical cell comprising a separator according to any of the embodiments of the first aspect of the application, or a separator prepared according to the method of any of the embodiments of the second aspect of the application.
In a fourth aspect the application provides an electrical device comprising an electrochemical cell according to the third aspect of the application.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be briefly described below; it is apparent that the drawings described below relate only to some embodiments of the present application and that other drawings may be obtained from the drawings without inventive work for those skilled in the art.
Fig. 1 is a schematic view of a separator according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present application clearer, the present application will be further described in detail with reference to examples. It should be understood that the examples described in this specification are for the purpose of illustrating the application only and are not intended to limit the application.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, when a composition is described as containing, comprising or including a particular component, or when a process is described as containing, comprising or including a particular process step, it is contemplated that the composition of the application also consists essentially of or consists of that component, and that the process of the application also consists essentially of or consists of that process step.
The use of the terms "comprising," "including," "containing," and "having" are generally to be construed as open-ended and not limiting, unless expressly stated otherwise.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, and the meaning of "multiple" in "one or more" is two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In the various examples, the list is merely a representative group and should not be construed as exhaustive.
Throughout this specification, substituents of a compound are disclosed in groups or ranges. It is expressly intended that such description include each individual subcombination of the members of these groups and ranges. For example, the term "C1-C6 alkyl" is expressly contemplated to disclose C1, C2, C3, C4, C5, C6, C1-C5, C1-C4, C1-C3, C1-C2, C2-C6, C2-C5, C2-C4, C2-C3, C3-C6, C3-C5, C3-C4, C4-C6, C4-C5, and C5-C6 alkyl individually.
As described in the background art, if the heat resistance and the adhesive property of the separator are not good during the preparation of the battery, wrinkles or blisters are easily formed on the surface of the electrode sheet after hot pressing, thereby deteriorating the safety performance of the battery. The provision of a release film that can be bonded at normal temperature is one of means for solving the above-mentioned problems.
The related art relates to a method for coating polymethyl methacrylate (PMMA) on the surface of a separation film so that the separation film can be attached to an electrode plate under a normal-temperature lamination process. In addition, due to the property of PMMA that can absorb electrolyte, the related art also relates to the use of PMMA to absorb electrolyte to form gel electrolyte, so as to reduce the safety risk brought by the conventional liquid organic electrolyte. However, PMMA has poor mechanical properties, resulting in a separator having mechanical properties that are difficult to meet the requirements of battery processing and use.
In view of this, the inventors have intensively studied and have made a lot of experiments to provide a separator, a method for producing the same, an electrochemical cell using the separator, and an electric device.
The first aspect of the application provides a separation film, which comprises a base film and a coating body distributed on at least one side of the base film, wherein the coating body comprises a fluid and a curing layer coated on the periphery of the fluid.
The fluid comprises a gel polymer electrolyte, the gel polymer electrolyte comprises a copolymerization product of a siloxane monomer and an acrylic ester monomer and an electrolyte adsorbed to the copolymerization product, and the copolymerization product has a hyperbranched structure. The cured layer is formed by curing the gel polymer electrolyte.
Without intending to be limited by any theory or explanation, the separator of the present application includes a base film and a coating body, can achieve normal temperature adhesion of the separator and an electrode sheet, and allows the separator to have good mechanical properties.
Specifically, the coating body comprises a fluid and a curing layer, wherein the curing layer is formed by curing the gel polymer electrolyte, and the curing layer can be broken to release the gel polymer electrolyte fluid in the normal-temperature lamination process of the isolating film and the electrode pole piece. The gel polymer electrolyte fluid can play a role of a binder, so that the isolating membrane and the electrode pole piece are firmly bonded together, and the normal-temperature bonding of the isolating membrane and the electrode pole piece is realized. In addition, the gel polymer electrolyte comprises a copolymerization product of a siloxane monomer and an acrylic monomer, wherein the copolymerization product is obtained by copolymerizing the siloxane monomer and an acrylic monomer and forming a hyperbranched structure. The molecular chain of the copolymerization product with the hyperbranched structure has a three-dimensional network structure, the molecular chain is not easy to be entangled, the viscosity is not obviously improved along with the increase of the molecular weight, and therefore, the mechanical property of the copolymerization product can be obviously improved, and the mechanical property of the isolation film is improved; and the copolymerization product can keep a viscous state at normal temperature, thereby being beneficial to the normal temperature adhesion of the isolating film and the electrode pole piece.
Moreover, the gel polymer electrolyte can replace liquid organic electrolyte, so that the isolating film is applied to a secondary battery, and the safety risk of the battery can be further reduced.
In the present application, the base film may be any material known in the art to be useful as a separator substrate, and may include, for example, a polyolefin porous separator, a nonwoven separator, an electrospun separator, and the like. The polyolefin porous membrane may be made of Polyethylene (PE) and/or polypropylene (PP), for example, a single-layer PE layer or PP layer structure, or a composite multi-layer structure of Polyethylene (PE) and polypropylene (PP).
The "coated body" described above may include coated dots or coated bodies having other shapes (e.g., bar, block, or other irregular shapes). The coating body on the surface of the separator may constitute a coating layer that is discontinuously distributed, for example, a plurality of coating bodies may be distributed in an island shape, constituting a coating layer that is discontinuously distributed.
The above-described "the cured layer is formed by curing the gel polymer electrolyte" may be achieved by means known in the art, and the curing means may include, but are not limited to, thermal curing or ultraviolet curing. When the curing means includes thermal curing or ultraviolet curing, the gel polymer electrolyte may further include thermal curing/ultraviolet curing functional groups and necessary auxiliaries. The thermally/uv curable functional groups may be groups contained in the molecules of the copolymerization product, and may include, for example, carbon-carbon double bonds; the necessary auxiliary agents may include, but are not limited to, at least one of a crosslinking agent, a catalyst for catalytic thermal curing or ultraviolet curing, an initiator. The selection of suitable functional groups and necessary auxiliaries is not limited herein, as long as the curing of the gel polymer electrolyte is acceptable to those skilled in the art.
The hyperbranched structures described above have meanings known in the art and can be characterized by methods known in the art. As an example, the T3 branching unit may be characterized by nuclear magnetic silica spectra to determine hyperbranched structures.
In some embodiments, the barrier film may satisfy a preset condition.
The preset conditions comprise: applying positive pressure to the barrier film through the test plate at 25 ℃; when the positive pressure born by the isolating film is 0.5-2MPa, the solidified layer breaks.
In the above-described preset condition, the test plate may include a test plate having a size greater than or equal to that of the separator. In some embodiments, a certain size of the isolation film can be cut as a test piece, whether the test piece meets a preset condition is determined, and the test result of the test piece is used as the test result of the isolation film. In some embodiments, the test piece may be placed on a horizontal test stand, a test plate placed on the surface of the test piece, and a positive pressure applied to the test piece. In some embodiments, the test piece may also be placed between two test plates, with a positive pressure applied to the test piece. The material of the test plate may be any material as long as it is satisfied that the plane in contact with the test piece is not significantly deformed when a positive pressure is applied to the test piece through the test plate, and the present application is not limited thereto. As an example, the material of the test panel may be aluminum, copper, stainless steel, rubber, plastic, a rubber-plastic material, or recycled leather or cardboard.
The preset conditions can be realized by controlling the hardness, thickness and other conditions of the cured layer. Those skilled in the art may choose an appropriate implementation according to actual needs, and is not limited herein.
Without intending to be limited by any theory or explanation, when the separator meets the preset conditions, the cured layer of the coated body can be more easily fractured when the separator is pressed with the electrode sheet at normal temperature in the battery processing process; after the solidified layer is broken, the internal fluid can be smoothly released, so that the isolating membrane is favorable for tightly bonding the electrode pole piece together through the fluid. When the isolating film meets the preset conditions, the risk of cracking of the solidified layer of the coating body in the isolating film winding process can be reduced.
In some embodiments, the siloxane monomer may comprise a combination of C10-C20 alkyl trimethoxysilane and gamma-methacryloxypropyl trimethoxysilane (KH-570).
In some embodiments, the C10-C20 alkyltrimethoxysilane may include at least one of dodecyltrimethoxysilane (WD-10), hexadecyltrimethoxysilane, octadecyltrimethoxysilane.
In some embodiments, the acrylic monomer may include an alkyl methacrylate, preferably at least one of methyl methacrylate, butyl methacrylate.
Without intending to be limited by any theory or explanation, the gamma-methacryloxypropyl trimethoxysilane can be copolymerized with an acrylic monomer to introduce polysiloxane segments into polymethyl methacrylate. And C10-C20 alkyl trimethoxy silane can form hyperbranched structure through silane hydrolytic condensation reaction with gamma-methacryloxypropyl trimethoxy silane, and introduces flexible alkyl chain segments. Thus, not only the strength of the copolymerization product is improved, but also the molecular chain flexibility of the copolymerization product is increased. Therefore, the physical and mechanical properties of the copolymerization product can be effectively improved, and the glass transition temperature of the copolymerization product can be reduced, so that the copolymerization product is in a viscous state with high viscosity at room temperature, the activity of the molecular chain of the copolymerization product is improved, and the ion conductivity of the diaphragm is further improved.
In some embodiments, the electrolyte may include an electrolyte lithium salt and an organic solvent.
The present application is not limited in the kind of the electrolyte lithium salt, and may include electrolyte lithium salts known in the art, for example, may include LiPF 6 LiFSI, etc. As an example, the electrolyte lithium salt may include LiPF 6 。
The present application is not limited in the kind of the organic solvent, and may include organic solvents known in the art to be useful for an electrolyte.
In some embodiments, the electrolyte lithium salt may be LiPF 6 The organic solvent may be selected from an organic solvent obtained by mixing Ethylene Carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) according to a volume ratio of 3:5:2, and the organic solvent may be selected from an organic solvent obtained by mixing Ethylene Carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) according to a volume ratio of 1:1:1, or at least one of an organic solvent obtained by mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) according to a volume ratio of 1:1:1. In the electrolyte, liPF 6 The concentration of (C) may be 0.8 to 1.2mol/L.
In some embodiments, the cured layer may be formed from a gel polymer electrolyte that is cured by ultraviolet light. Preferably, the gel polymer electrolyte may further include a photoinitiator.
The photoinitiator according to the present application is not limited in kind and may include photoinitiators known in the art to be useful for initiating the curing process of a monomer, oligomer or polymer matrix containing carbon-carbon double bonds under light induction. By way of example, the photoinitiator may include 2-hydroxy-2-methyl-1-phenyl-1-propanone (Irgacure 1173). In gel polymer electrolytes, the copolymerization product may contain carbon-carbon double bonds.
In some embodiments, the copolymerization product has a glass transition temperature Tg of 20℃or less, preferably Tg of 0 ℃. Therefore, the gel polymer electrolyte is favorable to keep a viscous state at room temperature, and the normal-temperature bonding of the isolating membrane and the electrode plate is facilitated.
A second aspect of the present application provides a method for preparing the release film of the first aspect, comprising the following steps S10 to S30.
S10, providing a gel polymer electrolyte, wherein the gel polymer electrolyte comprises a copolymerization product of a siloxane monomer and an acrylic ester monomer and an electrolyte adsorbed to the copolymerization product, and the copolymerization product has a hyperbranched structure.
In step S10, the silicone monomer and the acrylic monomer may be as described in the first aspect, and the embodiments of the silicone monomer and the acrylic monomer have been described and illustrated in detail above and are not repeated here.
And S20, coating, namely coating the gel polymer electrolyte on the surface of the base film to form a plurality of coating bodies on the surface of the base film.
In step S20, the coating process is not particularly limited, and may include a coating process known in the art. For example, a gravure roll may be used to apply a coating on the surface of the base film to form a plurality of coated bodies on the surface of the base film. In one example, as shown in fig. 1, spot coating may be performed on the surface of the base film 11 to form a coated body 12 having a substantially uniform shape and size and a substantially uniform distribution on the surface of the base film 11.
S30, a curing step, namely curing the gel polymer electrolyte on the surface of the coating body to obtain the isolating film.
In step S30, the curing means is not particularly limited, and may include, but is not limited to, thermal curing or ultraviolet curing. The curing layer formed after the surface layer of the coating body is cured can not be crushed by a winding process in the production of the isolating film, and a proper curing mode is selected according to actual needs on the premise that the curing layer can be crushed when the isolating film and the electrode pole piece are pressed at normal temperature, and curing parameters (such as heat curing temperature, heat curing time, ultraviolet light intensity, time exposed to ultraviolet light and the like) are adjusted according to actual needs.
The isolating film prepared by the method comprises a base film and a coating body, can realize normal-temperature bonding of the isolating film and the electrode pole piece, and has good mechanical properties.
Specifically, the cured coating body comprises fluid and a curing layer, wherein the curing layer is formed by curing the gel polymer electrolyte, and the curing layer can be broken to release the gel polymer electrolyte fluid in the normal-temperature lamination process of the isolating film and the electrode pole piece. The gel polymer electrolyte fluid can play a role of a binder, so that the isolating membrane and the electrode pole piece are firmly bonded together, and the normal-temperature bonding of the isolating membrane and the electrode pole piece is realized. In addition, the gel polymer electrolyte comprises a copolymerization product of a siloxane monomer and an acrylic monomer, wherein the copolymerization product is obtained by copolymerizing the siloxane monomer and an acrylic monomer and forming a hyperbranched structure. The molecular chain of the copolymerization product with the hyperbranched structure has a three-dimensional network structure, the molecular chain is not easy to be entangled, the viscosity is not obviously improved along with the increase of the molecular weight, and therefore, the mechanical property of the copolymerization product can be obviously improved, and the mechanical property of the isolation film is improved; and the copolymerization product can keep a viscous state at normal temperature, thereby being beneficial to the normal temperature adhesion of the isolating film and the electrode pole piece.
In some embodiments, providing a gel polymer electrolyte may include:
providing a copolymerization product.
And uniformly mixing the copolymerization product and the photoinitiator, and then soaking the mixture into the electrolyte so that the electrolyte is adsorbed on the copolymerization product to obtain the gel polymer electrolyte.
Preferably, the mass ratio of the copolymerization product to the photoinitiator is (100:1) - (100:8).
In some embodiments, a copolymerization product is provided, which may include in particular the steps of preparing a linear copolymer, preparing a hyperbranched copolymer, and capping as described below.
The step of preparing the linear copolymer comprises the steps of polymerizing acrylate monomers and gamma-methacryloxypropyl trimethoxy silane in the presence of an initiator to obtain the linear copolymer.
In this step, the initiator may be selected from radical initiators known in the art, and may be selected as desired by those skilled in the art, without limitation. In one embodiment, the initiator may comprise an organic peroxide initiator. The temperature of the reaction is not particularly limited, and in one embodiment, the reaction temperature may be 80 to 90 ℃.
The preparation of the hyperbranched copolymer comprises the steps of subjecting a linear copolymer, C10-C20 alkyl trimethoxysilane and gamma-methacryloxypropyl trimethoxysilane to hydrolytic condensation reaction in the presence of an organic acid to obtain the hyperbranched copolymer.
In the step, the molecular chain of the hyperbranched copolymer after hydrolytic condensation has a three-dimensional network structure and more crosslinking points, so that the strength of the polymer is improved; the C10-C20 alkyl trimethoxy silane with a flexible long chain can increase the flexibility of a polymer chain segment, effectively improve the physical and mechanical properties of the polymer, reduce the glass transition temperature of the polymer, keep the high-viscosity viscous state at room temperature, and increase the mobility of the polymer chain, thereby being beneficial to improving the ion conductivity of the diaphragm. In addition, gamma-methacryloxypropyl trimethoxysilane can reintroduce active double bonds at the periphery of the molecular chain of the hyperbranched copolymer, so that the hyperbranched copolymer can be further photocured. The reaction temperature for preparing the hyperbranched copolymer is not particularly limited, and in one embodiment, the reaction temperature may be 55 to 65 ℃.
And the end capping step comprises the step of mixing the hyperbranched copolymer with an end capping agent so as to enable the end capping agent to react with hydroxyl groups of the hyperbranched copolymer to obtain a copolymerization product.
In this step, the capping agent may be selected from radical capping agents known in the art, and may be selected as desired by those skilled in the art, without limitation. In one embodiment, the capping agent may include at least one of hexamethyldisiloxane, trimethylchlorosilane. The reaction temperature of the capping step is not particularly limited and in one embodiment, the reaction temperature may be 55-65 ℃.
By reacting the capping agent with Si-OH in the hyperbranched copolymer, the risk of further dehydration condensation of Si-OH can be reduced. Therefore, on one hand, the copolymerization product has proper crosslinking degree, so that the ionic conductivity of the copolymerization product is improved; on the other hand, the risk of side reaction between water generated by the hydrolysis condensation reaction of the silane and the electrolyte can be reduced, so that the risk of gas production of the electrolyte can be reduced, and the safety performance of the battery is improved.
In some embodiments, the step of preparing the linear copolymer may include:
100 parts by mass of acrylic monomer and 8-25 parts by mass of gamma-methacryloxypropyl trimethoxy silane are polymerized in the presence of 7-18 parts by mass of initiator to obtain linear copolymer.
In some embodiments, the initiator may be added to the reaction system by a staged batch process, for example, 100 parts by mass of the acrylate monomer and 8-25 parts by mass of the γ -methacryloxypropyl trimethoxysilane may be mixed uniformly in a suitable amount of solution (e.g., butyl acetate), half of the amount of the initiator is added, and after a period of reaction, the remaining amount of the initiator is added.
In some embodiments, the step of preparing the hyperbranched copolymer can include:
100 parts by mass of the linear copolymer and 2 to 25 parts by mass of C10-C20 alkyl trimethoxysilane are subjected to hydrolytic condensation reaction in the presence of an organic acid to obtain a mixed solution containing an intermediate product.
And adding 20-30 parts by mass of gamma-methacryloxypropyl trimethoxy silane into the mixed solution to enable the intermediate product and the gamma-methacryloxypropyl trimethoxy silane to undergo hydrolytic condensation reaction to obtain the hyperbranched copolymer.
The organic acid may be an aqueous acetic acid solution having ph=3, and the organic acid may be used in an amount of 40 to 47 parts by mass.
In some embodiments, the capping step may comprise:
100 parts by mass of the hyperbranched copolymer and 30-40 parts by mass of the end-capping agent are mixed so as to enable the end-capping agent to react with the hydroxyl groups of the hyperbranched copolymer, and a copolymerization product is obtained.
In one example, the capping agent may be prepared as a capping agent solution and then mixed with the hyperbranched copolymer. The capping agent solution may be prepared by the steps of: mixing 30-40 parts by mass of a blocking agent with a proper amount of absolute ethyl alcohol, heating to 60 ℃, slowly dropwise adding a hydrochloric acid aqueous solution with pH=3, and regulating the pH to 2.5-3.5 to obtain a blocking agent solution.
In some embodiments, the curing step may include:
exposing the coated body to a temperature of from 1 to 10mW/cm at a temperature of from 20 to 30 DEG C 2 And (3) under ultraviolet light for 1-3min to solidify the gel polymer electrolyte on the surface of the coating body to obtain the isolating film.
A third aspect of the application provides an electrochemical cell comprising a separator according to the second aspect of the application.
The electrochemical cell of the present application may be a primary cell or a secondary cell, and specific examples thereof include all kinds of lithium primary cells, lithium secondary cells or sodium cells. In particular, the lithium secondary battery includes a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
A fourth aspect of the application provides an electrical device comprising an electrochemical cell according to the third aspect of the application.
The electric device may be, but is not limited to, a mobile device (e.g., a cellular phone, a notebook computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship, a satellite, an energy storage system, etc.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Examples 1 to 5
(1) Methyl Methacrylate (MMA) monomer is alkali washed to remove the polymerization inhibitor and dried. 100 parts by mass of MMA, m 1 Adding KH-570 in a 500mL four-port bottle with a proper amount of solvent butyl acetate, introducing argon to remove oxygen in the bottle, heating to 85 ℃, condensing and refluxing, mechanically stirring, adding 8 parts by mass of dibenzoyl peroxide first, adding 8 parts by mass of dibenzoyl peroxide after 30min, continuing to react for 2h, placing in ice water after finishing, stopping the reaction, adding a proper amount of solvent butyl acetate for dilution, precipitating in petroleum ether, filtering, vacuum drying, dissolving in chloroform again, filtering, precipitating, and vacuum drying until the weight is unchanged, thus obtaining the linear copolymer.
(2) 100 parts by mass of a linear copolymer, m 2 Adding dodecyl trimethoxy silane and proper amount of tetrahydrofuran into a 500mL four-mouth bottle, stirring uniformly, heating to 60 ℃, and then dropwise adding m within 20 min 3 The reaction was continued for 12 hours after the completion of the reaction, with the aqueous acetic acid solution having ph=3. Subsequently add m 4 And (3) continuously reacting for 6 hours by using KH-570 in parts by mass, distilling under reduced pressure at 65 ℃ after the reaction is finished, and removing the solvent and water to obtain the viscous liquid hyperbranched copolymer.
(3) And (3) mixing 35 parts by mass of end-capping agent hexamethyldisiloxane with a proper amount of absolute ethyl alcohol under an argon atmosphere, adding the mixture into a 100mL four-neck flask, heating to 60 ℃, then slowly dropwise adding a hydrochloric acid aqueous solution with pH=3, adjusting the pH to 2.5-3.5, and preserving heat for 2 hours to obtain an end-capping agent solution. And (3) dissolving 100 parts by mass of hyperbranched copolymer in a proper amount of absolute methanol, heating to 60 ℃, slowly adding the end capping agent solution, continuing to react for 6 hours to obtain a white emulsion, standing for 12 hours, layering, taking down oily substances, and drying in vacuum to obtain a copolymerization product.
(4) Taking 100 parts by mass of a copolymerization product and m 5 The photoinitiator (Irgacure 1173) in parts by mass is stirred and mixed uniformly. Re-immersion in LiPF 6 In an electrolyte with a concentration of 1mol/L (the solvent is ECMixed solvent with the volume ratio of EMC to DMC of 1:1:1) to enable the copolymerization product to adsorb electrolyte, thus obtaining the gel polymer electrolyte.
(5) The surface of the PE film with the thickness of 7 mu m is coated by a coating gravure roller, so that the size of the coated gel polymer electrolyte is basically consistent and the distribution is uniform.
(6) At 25℃using 5 mW/cm 2 And (3) carrying out photo-curing on the surface layer of the point-coated gel polymer electrolyte for 2min to form a coating body on the surface of the PE film, thereby obtaining the isolating film.
(7) The separator was wound up to a winding contact pressure of 50N.
Comparative examples 1 to 2
Based on the procedure described in examples 1-5, the release films of comparative examples 1-2 were prepared according to the preparation parameters set forth in Table 1.
Test part
1) Air permeability test
The test was performed using a Wang Yan type air permeation instrument.
2) Bond strength
The coated surface of the release film was folded and pasted, and then the release film was fed into a plastic sealer using A4 paper with the temperature of the plastic sealer set to 100 ℃ and the speed set to 1. After plastic packaging, the test pieces were cut using a 2.5cm×30cm tooling die, tested on a pull-up tester at a speed of 50mm/min, and the average value was obtained three times.
3) Film surface condition test after compression
And observing whether the surface of the rolled isolating film has a fractured coating body and whether the film surface has an indentation.
4) Ion conductivity test
Assembled stainless steel/aerogel solid electrolyte separator/stainless steel symmetrical cell using 15 μl of electrolyte (LiPF 6 The concentration is 1mol/L; the solvent is a mixed solvent with a volume ratio of EC, DMC, DEC being 1:1:1), the bulk impedance R is tested, and calculated according to the ionic conductivity formula σ=l/(r×s), wherein σ is the ionic conductivity, S is the electrode contact area, and L is the isolation film thickness.
5) Testing of preset conditions
The release film was cut into 2.5cm by 30cm test pieces. At 25 ℃, a test plate (transparent acrylic plate, size of 5cm×50 cm) is fully covered on one surface of the test piece on which the coating body is arranged, a positive pressure with gradient increasing is applied to the test piece through the test plate, and the cracking condition of the solidified layer of the coating body is observed. Wherein the positive pressure is increased from 0 to 2MPa with a gradient of 0.1MPa, and the pressure is kept for 5min at each pressure value.
If the critical pressure P of the rupture of the solidified layer of the coating body on the surface of the test piece is 0.5-2MPa, the isolating film is considered to meet the preset condition.
The test results of examples 1-5 and comparative examples 1-2 are shown in Table 2.
TABLE 1 preparation parameters of the separators of examples 1-5 and comparative examples 1-2
TABLE 2 test results for examples 1-5 and comparative examples 1-2
Comparative analysis examples 1-5 and comparative examples 1-2 show that the barrier films of the present application, which exert a cohesive effect, are coated bodies, not coatings, and that the air permeability of the barrier films is not substantially adversely affected, all at a low level. The bond strength and ionic conductivity of the release film are mainly affected by the photoinitiator concentration and the mass fraction of siloxane monomers. On the one hand, comparative examples 1 to 5 and comparative example 1 found that PMMA without silicone modification rapidly cures into hard mass after photoinitiated polymerization, and cannot be fractured under a positive pressure of 2MPa, resulting in lower adhesive strength and ionic conductivity of the release film. On the other hand, comparative examples 1 to 5 and comparative example 2 show that the coating layer maintains a viscous state all the time when the gel polymer electrolyte does not have a photo-curing ability. Therefore, in the process of winding the isolating film, the coating body deforms after receiving the winding pressure, the initial morphology cannot be maintained, the adhesive effect is difficult to play, and the adhesive strength of the isolating film is low.
While the application has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the application. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (17)
1. A separator film, comprising:
a base film; and
a coating body distributed on at least one side of the base film;
wherein the coating body comprises a fluid and a curing layer coated on the periphery of the fluid;
the fluid comprises a gel polymer electrolyte, wherein the gel polymer electrolyte comprises a copolymerization product of a siloxane monomer and an acrylic ester monomer and an electrolyte adsorbed to the copolymerization product, and the copolymerization product has a hyperbranched structure;
the solidified layer is formed by solidifying the gel polymer electrolyte;
the barrier film satisfies preset conditions including: applying positive pressure to the separator through a test plate at 25 ℃; when the positive pressure born by the isolating film is 0.5-2MPa, the solidified layer breaks.
2. The separator as claimed in claim 1, wherein,
the siloxane monomers include a combination of a C10-C20 alkyl trimethoxysilane and a gamma-methacryloxypropyl trimethoxysilane; and/or
The acrylic monomer comprises alkyl methacrylate; and/or
The electrolyte includes an electrolyte lithium salt and an organic solvent.
3. The separator of claim 1, wherein the acrylic monomer comprises at least one of methyl methacrylate, butyl methacrylate.
4. The separator of claim 1, wherein the cured layer is formed from the gel polymer electrolyte by uv curing.
5. The separator of claim 4, wherein the gel polymer electrolyte further comprises a photoinitiator.
6. The separator according to any one of claims 1 to 5, wherein the glass transition temperature Tg of the copolymerization product is 20 ℃.
7. The separator according to any one of claims 1 to 5, wherein the glass transition temperature Tg of the copolymerization product is equal to or less than 0 ℃.
8. A method for producing the separator according to any one of claims 1 to 7, comprising:
providing a gel polymer electrolyte, wherein the gel polymer electrolyte comprises a copolymerization product of a siloxane monomer and an acrylic monomer and an electrolyte adsorbed to the copolymerization product, and the copolymerization product has a hyperbranched structure;
a coating step of coating the gel polymer electrolyte on a surface of a base film to form a coated body on the surface of the base film;
and a curing step, comprising curing the gel polymer electrolyte on the surface of the coating body to obtain the isolating film.
9. The method of claim 8, wherein said providing a gel polymer electrolyte comprises:
providing the copolymerization product;
and uniformly mixing the copolymerization product with a photoinitiator, and then soaking the mixture into electrolyte so that the electrolyte is adsorbed on the copolymerization product to obtain the gel polymer electrolyte.
10. The method of claim 8, wherein the mass ratio of the copolymerization product to the photoinitiator is (100:1) - (100:8).
11. The method of claim 9, wherein said providing said copolymerization product comprises:
the preparation of the linear copolymer comprises the steps of polymerizing acrylate monomers and gamma-methacryloxypropyl trimethoxy silane in the presence of an initiator to obtain the linear copolymer;
the preparation method of the hyperbranched copolymer comprises the steps of subjecting the linear copolymer, C10-C20 alkyl trimethoxysilane and gamma-methacryloxypropyl trimethoxysilane to hydrolytic condensation reaction in the presence of an organic acid to obtain the hyperbranched copolymer;
and a capping step, comprising mixing the hyperbranched copolymer with a capping agent to react the capping agent with hydroxyl groups of the hyperbranched copolymer to obtain the copolymerization product.
12. The method of claim 11, wherein the step of preparing a linear copolymer comprises:
100 parts by mass of acrylic monomer and 8-25 parts by mass of gamma-methacryloxypropyl trimethoxy silane are polymerized in the presence of 7-18 parts by mass of initiator to obtain linear copolymer.
13. The method of claim 11, wherein the step of preparing a hyperbranched copolymer comprises:
subjecting 100 parts by mass of the linear copolymer and 2-25 parts by mass of C10-C20 alkyl trimethoxysilane to hydrolytic condensation reaction in the presence of an organic acid to obtain a mixed solution containing an intermediate product;
and adding 20-30 parts by mass of gamma-methacryloxypropyl trimethoxy silane into the mixed solution to enable the intermediate product and the gamma-methacryloxypropyl trimethoxy silane to undergo hydrolysis condensation reaction to obtain the hyperbranched copolymer.
14. The method of claim 11, wherein the capping step comprises:
mixing 100 parts by mass of the hyperbranched copolymer with 30-40 parts by mass of a blocking agent to enable the blocking agent to react with hydroxyl groups of the hyperbranched copolymer, so as to obtain the copolymerization product.
15. The method according to any one of claims 9-14, wherein the curing step comprises:
exposing the coated body to a temperature of from 1 to 10mW/cm at from 20 to 30 DEG C 2 And (3) under ultraviolet light for 1-3min to solidify the gel polymer electrolyte on the surface of the coating body to obtain the isolating film.
16. An electrochemical cell comprising a separator according to any one of claims 1-7, or a separator prepared according to the method of any one of claims 8-15.
17. An electrical device comprising the electrochemical cell of claim 16.
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